EP0933405A1 - Wässrige Tintenzusammensetzung, Verfahren zur Herstellung und Aufzeichnung mittels dieses Tintenstrahls - Google Patents

Wässrige Tintenzusammensetzung, Verfahren zur Herstellung und Aufzeichnung mittels dieses Tintenstrahls Download PDF

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Publication number
EP0933405A1
EP0933405A1 EP19990102096 EP99102096A EP0933405A1 EP 0933405 A1 EP0933405 A1 EP 0933405A1 EP 19990102096 EP19990102096 EP 19990102096 EP 99102096 A EP99102096 A EP 99102096A EP 0933405 A1 EP0933405 A1 EP 0933405A1
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EP
European Patent Office
Prior art keywords
ink
composition
urea
ppm
aqueous ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19990102096
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English (en)
French (fr)
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EP0933405B1 (de
Inventor
Keiichi Mukaiyama
Hiroshi Mukai
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Seiko Epson Corp
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Seiko Epson Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the invention relates to aqueous ink compositions which are stably ejected in a jet for an extended period of time, a process for preparing the same, and an ink jet recording method using the same. More particularly, it relates to an aqueous ink composition which is stable in ejecting through ink jet nozzles in an ink jet recording and to a process for preparing ink having improved ejecting properties.
  • An ink jet recording unit is mounted on a computer terminal, a printing calculator, a facsimile, or similar device.
  • the printing performance of the ink jet recording unit is largely governed by the nature and quality of the ink. For example, if an ink component coagulates as a result of water evaporation from the ink, or if a material forming the ink path through the ink jet head dissolves and precipitates in ink, the ink jet nozzles can become clogged and fail to eject ink droplets.
  • JP-A-9-123437 teaches adding urea to ink compositions to improve water retention. According to the technique disclosed, evaporation of the water content is suppressed to prevent the ink component from coagulation. Also, the solubility of the material constituting the ink path through the ink jet head is increased to prevent the material from precipitating.
  • addition of urea to ink compositions is effective in preventing clogging of the ink eject, it has been learned that urea can decompose to detrimentally alter the ink composition or its physical properties. This can result in deteriorated printing quality when a urea-containing ink composition is left to stand at high temperatures or for extended periods at moderate temperatures. It has hence been proposed to add not only urea but ammonium ions to ink compositions thereby suppressing urea decomposition as disclosed in JP-A-5-17714.
  • the present invention provides aqueous ink compositions containing an azo dye and urea which maintains high printing performance while preventing bubble formation in the course of use.
  • the invention provides a process for preparing such aqueous ink compositions.
  • the invention provides an ink jet recording method using such aqueous ink compositions.
  • the invention provides an aqueous ink composition comprising urea, a colorant comprising an azo dye, and water.
  • a preferred composition has a dissolved ammonium ion concentration of not more than 200 ppm, and a dissolved nitrogen content of not more than 5 ppm.
  • urea as used herein includes not only urea itself, but analogous compounds such as thiourea.
  • aqueous ink as used herein denotes not only inks containing water as the sole solvent, but also those containing mixed solvents such as water and a water-soluble organic solvent.
  • a colorant comprising an azo dye, and water
  • the ink can contain other components, such as viscosity modifies and rust inhibitors, if desired.
  • Fig. 1 is a graph showing the relationship between ammonium ion concentration and solubility of nitrogen in ink compositions.
  • Fig. 2 is a schematic view of an ink jet recording unit.
  • Fig. 3 is a partial cross section of an ink jet head.
  • Fig. 4 is a flow chart of a particular process for preparing aqueous ink compositions.
  • aqueous ink composition containing a colorant comprising an azo dye and urea When an aqueous ink composition containing a colorant comprising an azo dye and urea is allowed to stand at high temperature, or for long periods at more moderate temperature, the azo dye can decompose to form molecular nitrogen (N 2 ), and the urea can decompose to form ammonium ions (NH 4 + ). At an ink composition pH of 7 or higher, the ammonium ions can produce free ammonia (NH 3 ). As seen in the relationship between ammonium ion concentration and solubility of nitrogen depicted in Fig. 1, as ammonium ion concentration increases, the amount of nitrogen that can dissolve in ink decreases.
  • the ammonium ion concentration can be reduced by blowing nitrogen through the prepared ink as described below.
  • the ammonium ion concentration can be controlled by adjusting the amount of urea added, thereby substantially preventing bubble formation.
  • the amount of added urea is limited within a range of from about 0.2 to about 2.4% by weight, it is possible to maintain the initial ammonium ion concentration to 200 ppm or below without conducting the step of blowing nitrogen. With the ammonium ion concentration kept lowered in this way, the solubility of nitrogen can be maintained at a high level. Bubble formation in ink is thus avoided for a prolonged period of time merely by degassing prepared ink to adjust the initial dissolved nitrogen content to 5 ppm or below. While the amount of added urea should be minimized to prevent bubble formation, it is desirable to add urea in an amount of at least about 0.2% by weight to prevent jet nozzle clogging.
  • the aqueous ink according to the present invention can be prepared by a process comprising the steps of: a) blowing nitrogen through an ink composition comprising urea, a colorant comprising an azo dye, and water, thereby releasing free ammonia from the composition and concurrently reducing the dissolved ammonium ion concentration, b) degassing the resulting composition to release nitrogen, and c) filling an ink container with the resulting composition.
  • a reduction in ammonium ion concentration is achieved in the course of ink composition preparation by using nitrogen, which can be removed later by an easy operation such as degassing with another gas, such as argon for example, or by exposing the composition to reduced pressure.
  • nitrogen which can be removed later by an easy operation such as degassing with another gas, such as argon for example, or by exposing the composition to reduced pressure.
  • the step of blowing nitrogen is preferably carried out until the dissolved ammonium ion concentration in the prepared ink composition decreases to 200 ppm or lower.
  • the step of degassing is preferably carried out until the dissolved nitrogen content in the prepared ink decreases to 5 ppm or lower.
  • the pH of the prepared ink be adjusted to a value of from about 7 to about 10 so that borosilicate glass, which can constitute part of the ink flow path of the ink jet head does not dissolve.
  • borosilicate glass which can constitute part of the ink flow path of the ink jet head does not dissolve.
  • ammonium ion is converted to free ammonia, and the amount of nitrogen that can dissolve in the ink decreases, tending to lead to nitrogen supersaturation.
  • the ink according to the present invention is free from nitrogen supersaturation during use because the initial ammonium ion and nitrogen concentrations have been reduced to low levels, as desribed above.
  • the aqueous ink compositions of the invention do not suffer from bubble formation upon being subjected to pressure shocks resulting from a ejecting operation, they are well suited to ink jet recording in which the ink composition is ejected in a jet from ink jet nozzles onto a recording medium. Even where part of the ink path of the ink jet nozzles is made of borosilicate glass, the urea present in the inventive ink composition prevents the glass components from being coated with precipitants and causing clogging of the nozzles.
  • Fig. 2 is a schematic illustration of an ink jet recording unit.
  • Ink jet recording unit 1 has ink jet head 2 mounted on carriage 5. Carriage 5 reciprocates to carry out the printing of letters and images on recording paper 7 held on platen 6.
  • Ink tank (or ink container) 9 containing a printing ink composition is connected to ink jet head 2 via ink feed tube 8.
  • Ink jet recording unit 1 has cap 3 that is capable of covering the nozzles of head 2, and pump 4 is connected to cap 3 through discharge tube 10. On operating pump 4 with the nozzles of head 2 covered with cap 3, bubbles and ink are drawn to cap 3 from the nozzles of head 2, and the drawn ink is held in an ink absorber (not shown) in cap 3 and then discharged into spent ink reservoir 11.
  • the ink jet recording unit shown in Fig. 2 has been described with respect to use of the ink composition of the invention in an off-carriage type in which ink jet head 2 and ink tank 9 are separate members that are connected with a tube
  • the ink composition of the invention is applicable as well to an ink jet recording unit of on-carriage type in which an ink jet head and an ink tank are integrally molded and mounted on a carriage. Since the ink of the invention is prevented from undergoing a viscosity increase and forming bubbles, the cap for covering the ink jet head as used in the ink jet recording unit of Fig. 2 can be omitted depending on the mode or condition of use of a recording unit.
  • Fig. 3 is a partial cross section of ink jet head 2 of the edge ink jet type.
  • Ink jet head 2 comprises cover plate 202 made of glass, cavity plate 203 made of a p-type silicon plate, and glass substrate 204. These plates are bonded together in this order as shown.
  • a plurality of runners is formed at the edge of cavity plate 203 to form an equal number of nozzles 221.
  • Cavity plate 203 is shaped to have recesses. Each recess provides pressure chamber 206, the bottom of which functions as vibrating plate 205.
  • Fine runners 208 are present at the rear of each recess and a recess forming ink reservoir 210 serves to feed ink to individual pressure chambers 206.
  • Ink reservoir 210 has ink feed hole 224 connecting to ink feed tube 8 (Fig. 2), and ink is fed thereto from ink tank 9 (Fig 2).
  • the fed ink composition is initially reserved in ink reservoir 210.
  • the lower side of cavity plate 203 has a mirror finish and attached to glass substrate 204.
  • Glass substrate 204 has recesses, each of which functions as vibration chamber 212 at positions corresponding to individual vibrating plates 205.
  • Each recess of glass substrate 204 has an electrode 214 which faces its respective vibrating plate 205. Recording signals are sent from the drive to electrode 214, vibrating plate 205 vibrates by electrostatic force, and the vibration energy varies the inner pressure of pressure chamber 206, thereby ejecting an ink droplet from nozzle 221.
  • the ink composition is supersaturated with nitrogen in ink jet head 2, bubbles are generated by shocks, such as a pressure shock from ejecting. Bubbles formed absorb the ink ejecting energy, resulting in a failure to stably eject the ink composition.
  • shocks such as a pressure shock from ejecting. Bubbles formed absorb the ink ejecting energy, resulting in a failure to stably eject the ink composition.
  • Fig. 4 is a flow chart of the process steps according to the invention, which comprises steps 1 through 5.
  • Step 1 is a weighing step in which the ink constituent materials are weighed out.
  • Step 2 is a mixing step in which the weighed materials are mixed by stirring while cooling, i.e., at or below room temperature. Cooling suppresses the decomposition of urea and production of ammonium ions to some extent, but partial decomposition of urea to produce ammonium ions can not be avoided completely.
  • an ink composition having the above composition has a dissolved ammonium concentration of about 180 ppm when prepared at ambient temperature.
  • step 3 nitrogen is blown through the mixture to release free ammonia (nitrogen blowing step). Part of the ammonium ions are converted to free ammonia at a pH of 7 or higher. Free ammonia is released in the atmosphere upon blowing nitrogen, i.e., supersaturation with nitrogen, to decrease the dissolved ammonium concentration by about 20 to 30%.
  • step 4 the mixture from step 3 is exposed to reduced pressure to remove nitrogen (degassing step).
  • the mixture is allowed to stand at room temperature in a reduced pressure atmosphere (for example 10 mmHg for about 20 seconds) to reduce the dissolved nitrogen content to 5 ppm or lower.
  • step 5 the mixture from step 4 is poured into an ink container, which may be a tank, a bag or a cartridge.
  • the ink composition and/or preparation are illustrated as providing an aqueous ink composition which does not tend to become supersaturated with nitrogen.
  • Aqueous ink compositions prepared by the process according to the invention are not particularly limited in compounding components and compounding ratios as long as they comprise urea, a colorant comprising an azo dye, and water and does not have an ammonium ion as a counter ion.
  • a typical example of a useful ink composition is shown below. All the parts are given by weight.
  • Acetylene glycol type surfactant 3.2 parts
  • Urea 1.8 parts Water 75.5 parts
  • aqueous ink thus prepared is protected from evaporation of water because of urea and therefore is not prone to nozzle clogging, such as that resulting from the coagulation of ink components.
  • urea in the ink composition increases the solubility of glass components dissolved from borosilicate glass typically used as a material in ink paths. Therefore, the dissolved glass components do not tend to precipitate in the nozzles and clogging of the nozzles is thereby avoided.
  • Example 1 the dissolved ammonium ion concentration of the prepared ink composition was reduced by blowing nitrogen to 200 ppm or lower irrespective of the compounding ratio of urea.
  • the ink composition according to Example 1 had its dissolved nitrogen content and ammonium ion concentration established at much lower levels than 5 ppm and 200 ppm, respectively, in the initial stage of its service life. Even if urea in the ink decomposes to produce ammonium ions, thereby reducing the solubility of nitrogen, the amount of nitrogen produced from an azo dye in this case would not supersaturate the ink.
  • the ammonium ions if produced upon urea decomposition during use of the ink, never exceeds about 800 ppm. Even though water partly evaporates from the ink, the nitrogen concentration of the ink can be adjusted to about 7 ppm or lower. With the nitrogen concentration so low, printing defects due to bubbles do not occur. According to Example 1, nitrogen does not reach supersaturation even in the presence of urea so that bubbles do not tend to form. Therefore, the aqueous ink composition obtained in Example 1, when used in an ink jet recording unit, maintains its high printing performance without frequent maintenance operations, such as priming, pumping, flushing, and the like.
  • a preferred compounding ratio of urea is not more than 2.4% by weight for controlling the ammonium ion concentration while securing sufficiently high water retention.
  • Example 2 While in Example 1, the initial ammonium ion concentration of the aqueous ink composition is reduced to a suitably low level by the step of blowing nitrogen, in Example 2 the ammonium ion concentration is adjusted by controlling the amount of urea added. That is, the urea content of the aqueous ink composition, which comprises urea, a colorant comprising an azo dye, and water and which does not have an ammonium ion as a counter ion, is restricted within a range of from about 0.2 to about 2.4% by weight. A typical ink composition according to Example 1 was prepared.
  • the urea content is as low as about 0.2 to about 2.4% by weight, the ammonium ion concentration does not exceed 200 ppm so that the solubility of nitrogen can be kept high without the step of blowing nitrogenas conducted in Example 1.
  • Ink A having the following basic formulation (all the parts are by weight) was prepared at room temperature.
  • the components of the ink composition according to Example 1 were mixed at room temperature, and the mixture was subjected to degassing to give prepared ink composition B having an initial dissolved ammonium ion concentration of 200 ppm or less and an initial dissolved nitrogen content of 5 ppm or less.
  • Ink C was prepared at 98°C by adding 4.8 parts by weight of urea to the above basic formulation.
  • An ink jet head was filled with each of ink A and ink C and allowed to stand at 60°C for 5 days with its nozzles uncapped (open to air). Thereafter printing was carried out. Dot missing attributed to clogging of the nozzles was not observed with ink C containing urea whereas dot missing occurred with ink A containing no urea.
  • an ink jet head was filled with ink C and allowed to stand at 60°C for 9 days with its nozzles capped and then at 25°C and 30% RH (relative humidity) for 14 days with its nozzles open to air. When printing was carried out thereafter, formation of bubbles in the ink was observed.
  • Ink composition B was charged in an ink jet head in the same manner as for ink composition A and ink composition C. After leaving the ink jet head uncapped at 60°C for 5 days, printing was carried out. As a result, it was observed that no dots were missing from the print substrate due to clogging of the nozzles. Even after ink composition B charged in the ink jet head was allowed to stand at 60°C for 9 days with the nozzles capped and then at 25°C and 30% relative humidity for 14 days with the nozzles uncapped, printing was carried out normally without evidence of bubble formation in the ink.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
EP19990102096 1998-02-02 1999-02-02 Wässrige Tintenzusammensetzung, Verfahren zur Herstellung und Aufzeichnung mittels dieses Tintenstrahls Expired - Lifetime EP0933405B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP02054998A JP4168465B2 (ja) 1998-02-02 1998-02-02 水溶性インク、水溶性インクの製造方法、およびインクジェット記録方法
JP2054998 1998-02-02

Publications (2)

Publication Number Publication Date
EP0933405A1 true EP0933405A1 (de) 1999-08-04
EP0933405B1 EP0933405B1 (de) 2003-05-07

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EP19990102096 Expired - Lifetime EP0933405B1 (de) 1998-02-02 1999-02-02 Wässrige Tintenzusammensetzung, Verfahren zur Herstellung und Aufzeichnung mittels dieses Tintenstrahls

Country Status (6)

Country Link
US (1) US6086660A (de)
EP (1) EP0933405B1 (de)
JP (1) JP4168465B2 (de)
CN (1) CN1195807C (de)
DE (1) DE69907527T2 (de)
HK (1) HK1022327A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1184428A1 (de) * 2000-09-01 2002-03-06 Ricoh Company, Ltd. Flüssige Pigmentdispersion und Verfahren zu deren Herstellung

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6726754B2 (en) * 2002-09-13 2004-04-27 Kimberly-Clark Worldwide, Inc. Method for enzyme mediated removal of gas from inks, and reduced gas inks
DE602004023856D1 (de) * 2003-08-11 2009-12-10 Canon Kk Tinte, aufzeichnungsverfahren, aufzeichnungseinheit, tintenpatrone und aufzeichnungsgerät
JP3848352B2 (ja) * 2004-07-02 2006-11-22 キヤノン株式会社 インクジェット用ブラックインク、インクセット、インクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP3885086B2 (ja) * 2004-07-02 2007-02-21 キヤノン株式会社 インクジェット用ブラックインク、インクセット、インクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP6236823B2 (ja) * 2013-03-22 2017-11-29 セイコーエプソン株式会社 インクジェット記録方法
JP2016172336A (ja) * 2015-03-16 2016-09-29 セイコーエプソン株式会社 インクジェット記録方法
JP7228123B2 (ja) 2018-09-25 2023-02-24 セイコーエプソン株式会社 インクジェットインク組成物、インクパック、及びインクジェット記録方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2055116A (en) * 1979-06-22 1981-02-25 Canon Kk Recording liquid composition
EP0612820A2 (de) * 1993-02-26 1994-08-31 Canon Kabushiki Kaisha Tinte, Tintenstrahlaufzeichnungsverfahren und -vorrichtung
EP0790127A2 (de) * 1995-08-28 1997-08-20 Seiko Epson Corporation Tintenstrahldrucker und Tinte für die Tintenstrahlaufzeichnung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5092926A (en) * 1988-10-03 1992-03-03 Seiko Epson Corporation Ink-jet printing ink
JP3123662B2 (ja) * 1991-07-08 2001-01-15 キヤノン株式会社 インクジェット記録用インク、これを用いたインクジェット記録方法及びかかるインクを用いた機器
US5755861A (en) * 1995-05-19 1998-05-26 Brother Kogyo Kabushiki Kaisha Ink composition, process for its preparation, and ink-jet recording process
US5637138A (en) * 1995-06-06 1997-06-10 Brother Kogyo Kabushiki Kaisha Ink composition, process for its preparation, and ink-jet recording process
JPH0931378A (ja) * 1995-07-17 1997-02-04 Brother Ind Ltd 記録用インク
JPH0931376A (ja) * 1995-07-17 1997-02-04 Brother Ind Ltd 記録用インク

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2055116A (en) * 1979-06-22 1981-02-25 Canon Kk Recording liquid composition
EP0612820A2 (de) * 1993-02-26 1994-08-31 Canon Kabushiki Kaisha Tinte, Tintenstrahlaufzeichnungsverfahren und -vorrichtung
EP0790127A2 (de) * 1995-08-28 1997-08-20 Seiko Epson Corporation Tintenstrahldrucker und Tinte für die Tintenstrahlaufzeichnung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1184428A1 (de) * 2000-09-01 2002-03-06 Ricoh Company, Ltd. Flüssige Pigmentdispersion und Verfahren zu deren Herstellung
US6565642B2 (en) 2000-09-01 2003-05-20 Ricoh Company, Ltd. Pigment dispersion liquid and method of producing the same

Also Published As

Publication number Publication date
CN1231314A (zh) 1999-10-13
US6086660A (en) 2000-07-11
HK1022327A1 (en) 2000-08-04
DE69907527T2 (de) 2004-03-18
JP4168465B2 (ja) 2008-10-22
CN1195807C (zh) 2005-04-06
JPH11217527A (ja) 1999-08-10
DE69907527D1 (de) 2003-06-12
EP0933405B1 (de) 2003-05-07

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